Process for the manufacture of 2-chloro-3,3,3-trifluoropropene by gas phase fluorination of pentachloropropane

ABSTRACT

The present invention provides a process of catalytic fluorination in gas phase of product 1,1,1,2,3- pentachloropropane or/and 1,1,2,2,3-pentachloropropane into product 2-chloro-3,3,3-trifluoropropene in presence of a catalyst and oxygen.

FIELD OF THE INVENTION

The aim of the invention is the catalytic fluorination in gas phase ofproduct 1,1,1,2,3-pentachloropropane (HCC 240 db) and/or1,1,2,2,3-pentachloropropane (HCC 240aa) into product2-chloro-3,3,3-trifluoropropene (HCFO 1233xf).

TECHNICAL BACKGROUND

The protocol of Montreal for the protection of the ozone layer led tothe end of the use of chlorofluorocarbons (CFCs). Less aggressivecompounds for the ozone layer, such as the hydrofluorocarbons (HFCs)e.g. HFC-134a replaced chlorofluorocarbons. These latter compounds wereindeed shown to provide greenhouse gases. There exists a need for thedevelopment of technologies, which present a low ODP (ozone depletionpotential) and a low GWP (global warming potential).

Although the hydrofluorocarbons (HFCs), which are compounds which do notaffect the ozone layer, were identified as interesting candidates, theyexhibit a relatively high GWP value. There still exists the need to findcompounds which exhibit a low GWP value. Hydrofluoroolefins (HFO) wereidentified as being possible alternatives with very low ODP and GWPvalues.

Several processes for production of HFOs compounds, in particular ofpropenes, were developed. The two compounds 1233xf(2-chloro-3,3,3-trifluoropropene) and 1234yf(2,3,3,3-tetrafluoropropene) are particularly desired.

US2009/0240090 discloses the gas-phase reaction of1,1,1,2,3-pentachloropropane (HCC 240 db) into product2-chloro-3,3,3-trifluoropropene (HCFO 1233xf), in the absence of oxygen.Example 3 uses a catalyst comprised of fluorinated Cr₂O₃. The product1233xf thus produced is then converted into product2-chloro-1,1,1,2-tetrafluoropropane (244bb) in a liquid phase reaction.

WO2009/015317 discloses the reaction of a chlorinated compound, whichcan be 1,1,2,3-tetrachloro-1-propene (1230xa),1,1,1,2,3-pentachloropropane (240 db) or 2,3,3,3-tetrachloro-1-propene(1230xf) with HF, in gas phase, on a catalyst and in the presence of atleast one stabilizer. This process allows obtaining2-Chloro-3,3,3-trifluoro-1-propene (1233xf). No working example isprovided with 240 db as a starting material. The stabilizer is said toimprove catalyst lifetime. It is also mentioned that periodicregeneration is considered.

WO2005/108334, example 3, discloses that 240 db is passed through a flowreactor for a contact time for about 5 to 50 seconds at about 250-400°C. in the presence of 5 molar excess of HF over a 50 g ⅛-inch Cr₂O₃catalyst bed to give 244 db (2-chloro-1,1,1,3-tetrafluoropropane). It isfurther indicated that the 244 db is then dehydrochlorinated by passingit over a Cr₂O₃ catalyst (50 g) at 425-550° C. with a contact time of 25to seconds to afford product 1234ze (1,3,3,3-tetrafluoropropene).

GB-A-1091103 discloses a process for manufacturing a chromiumfluorination catalyst. Numerous compounds that may be fluorinated usingthis catalyst are indicated: pentachloropropane is mentioned amongothers, while not being the preferred compound.

Thus, there is still a need for processes for the production of compound1233xf.

SUMMARY OF THE INVENTION

The invention provides a process of catalytic fluorination in gas phaseof product 1,1,1,2,3-pentachloropropane or/and1,1,2,2,3-pentachloropropane into product2-chloro-3,3,3-trifluoropropene in presence of a catalyst and oxygen.

Embodiments are the following:

-   -   The ratio of oxygen with respect to pentachloropropane (240) is        0.05 to 15 mole %, preferably 0.5 to 10 mole %.    -   The process is carried out in the presence of a catalyst        comprising Ni—Cr, preferably supported.    -   The catalyst is supported on a support selected from fluorinated        alumina, fluorinated chromia, fluorinated activated carbon or        graphite carbon.    -   The catalyst further comprises a co-catalyst selected from Ni,        Co, Zn, Mn or mixtures thereof, preferably nickel, and wherein        said co-catalyst is preferably present in an amount from about        1-10 wt % of said fluorination catalyst.    -   The fluorination catalyst is activated with a        fluorine-containing compound, preferably hydrogen fluoride, and        preferably at a pressure above 10 bars.    -   The 1,1,1,2,3-pentachloropropane contains up to 40 mol % of        isomer 1,1,2,2,3-pentachloropropane.    -   The process is carried out at a pressure from 1 to 20 bars,        preferably 3 to 15 bars, more preferably 5 to 10 bars.    -   The process is carried out at a temperature of from 200 to 450°        C., preferably from 300 to 430° C., more preferably from 320 to        420° C.    -   The process is carried out with a contact time from 6 to 100        sec, preferably from 10 to 80 sec, more preferably from 15 to 50        sec.    -   The process is carried out with a molar ratio HF:240 from 3:1 to        150:1, preferably 4:1 to 70:1, more preferably 5:1 to 50:1.    -   The process is carried out in the presence of a polymerization        inhibitor, preferably chosen from the group consisting of        p-methoxyphenol, t-amylphenol, limonene, d,1-limonene, quinones,        hydroquinones, epoxides, amines and mixtures thereof. The        invention relates to also the products obtained by following the        steps of the process disclosed herewith, in particular a mixture        containing mainly 1233xf and impurities and/or unreacted        starting materials and/or co-products.

DETAILED DESCRIPTION OF EMBODIMENTS

The invention is based on the findings that 240 db (and/or 240aa) can becatalytically fluorinated in gas phase into 1233xf, and that processconditions can be selected so as to achieve a reaction with an improvedcatalyst lifetime, when oxygen is cofed with 240.

Product 240aa will be converted in part into the desired product whilethe by-products which are presumably of the 243 type can be usedusefully in other reactions. Hence, even if starting material 240aa isnot completely converted into the desired 1233xf, the products formedotherwise have value.

The catalyst used in the invention is for example a catalyst based on ametal including a transition metal oxide or a derivative or halide oroxyhalide such a metal. Catalysts are e.g. FeCl₃, chromium oxyfluoride,chromium oxides (that can optionally be subject to fluorinationtreatments), chromium fluorides, and mixtures thereof. Other possiblecatalysts are the catalysts supported on carbon catalysts based onantimony, catalysts based on aluminum (as AlF₃ and Al₂O₃ and oxyfluorideof alumina and aluminum fluoride). Generally speaking, catalysts thatcan be used are chromium oxyfluoride, aluminium fluorure andoxyfluoride, and supported or unsupported catalyst containing a metalsuch as Cr, Ni, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb, Mg. Reference can also bemade to the disclosures of WO-A-2007/079431, at page 7, lines 1-5 and28-32, EP-A-939071, at paragraph [0022], WO2008/054781 at page 9 line 22to page 10 line 34, WO2008/040969 in claim 1, all incorporated herein byreference.

Prior to its use, the catalyst is subjected to activation, typicallywith HF at high pressure, typically above about 10 bars (typically at apressure above the pressure used in the gas-phase process), as describedin U.S. Pat. No. 7,485,598, incorporated herein by reference. Anysuitable conditions would also be appropriate.

A preferred embodiment uses a particular catalyst, which is a mixedcatalyst, containing both chromium and nickel. The molar ratio Cr: Ni,with respect to the metallic element is generally between 0.5 and 5, forexample between 0.7 and 2, including close to 1. The catalyst maycontain in weight from 0.5 to 20% chromium and 0.5 to 20% nickel,preferably between 2 and 10% of each metal.

The metal may be present in metallic form or as derivatives, includingoxide, halide or oxyhalide. These derivatives, including halide andhalide oxides, are obtained by activation of the catalytic metal.Although the activation of the metal is not necessary, it is preferred.

The support is preferably made from aluminum. There are several possiblecarriers such as alumina, activated alumina or aluminum derivatives.These derivatives include aluminum halides and halide oxides ofaluminum, for example described in U.S. Pat. No. 4,902,838, or obtainedby the activation process described below.

The catalyst may include chromium and nickel in a non-activated oractivated form, on a support that has been subjected to activation ornot.

Reference can be made to WO2009/118628, and especially to the disclosureof the catalyst from page 4, line 30 to page 7, line 16, which isincorporated herein by reference.

The catalyst can also be a high surface area Cr based catalyst which ispreferably unsupported. The catalyst can optionally contain a low levelof one or more co-catalyst such as Co, Zn, Mn, Mg and Ni salt. Apreferred co-catalyst is nickel. Another preferred co-catalyst is Zn.Another preferred co-catalyst is Mg.A disclosure of the high surfacearea Cr based catalyst can be found in WO2009/158321, pages 4 and 6).The process of the present invention is preferably run continuously.

The present fluorination process involves contacting 240 db with HF inthe reaction zone in a gas phase, under conditions sufficient to convertthe 240 db to fluorination products comprising mainly 1233xf.

Typically, the process of the invention is carried out with a molarratio HF:240 from 3:1 to 150:1, preferably 4:1 to 70:1, more preferably5:1 to 50:1.

Typically, the process of the invention is carried out at a pressurefrom 1 to 20 bars, preferably 3 to 15 bars, more preferably 5 to 10bars.

Typically, the process of the invention is carried out at a temperatureof from 200 to 450° C., preferably from 300 to 430° C., more preferablyfrom 320 to 420° C. The temperature of the bed can be substantiallyuniform in the reactor or can be adjusted along the path of the stream,decreasing or increasing along the direction of flow.

Contact times (catalyst volume divided by the total flow rate ofreactants and co-feeds, adjusted to the operating pressure andtemperature) are typically from 6 to 100 sec, preferably from 10 to 80sec, more preferably from 15 to 50 sec.

An oxygen co-feed is used to extend the catalyst lifetime, typically inan amount of from 0.05 to 15 mole o, preferably 0.5 to 10 mole % ofoxygen or chlorine per pentachloropropane molecule. The oxygen can beintroduced as an oxygen-containing gas such as air, pure oxygen, or anoxygen/nitrogen mixture.

A polymerization inhibitor can be used to extend the catalyst life,typically in a concentration of from about 50-1000 ppm, more preferablybetween 100-500 ppm. The polymerization inhibitor can bep-methoxyphenol, t-amylphenol, limonene, d,1-limonene, quinones,hydroquinones, epoxides, amines and mixtures thereof. The preferredpolymerization inhibitor is p-methoxyphenol or t-amylphenol. Theco-feeding of a low level of a polymerization inhibitor can control suchpolymerization of chloroolefins and extend the life of the catalyst asdescribed in U.S. Pat. No. 5,714,651, incorporated herein by reference.

The reactants can be fed to the reactor at the same location, atdifferent locations, or using staged feeding at staged locations alongthe reactor. A preferred feeding system is to blow the gaseous reactantsat the bottom of the reactor. Recycling can be done at the entry of thereactor or at an intermediate stage of the reactor; preferably at theentry of the reactor. It is also possible to recycle part of the streamexiting the reactor.

Reactions are implemented in a dedicated reactor for reactions involvinghalogens. Such reactors are known to those skilled in the art and caninclude linings based eg Hastelloy®, Inconel®, Monel® or fluoropolymers.The reactor may also include means of heat exchange, if necessary.

The final product is readily recovered by any means known in the art,such as by scrubbing, washing, extraction, decantation and preferablydistillation. It can also be further purified by distillationtechniques.

EXAMPLES

The following examples illustrate the invention without limiting it.

The equipment used consists of a tubular reactor of an internal diameterof 19 mm, made of INCONEL® alloy 600 surrounded by a tubular oven. It isalso equipped with pressure and temperature controller. The reactants,preliminarily vaporized thanks a heater, are introduced in gaseous phaseat the top of the reactor.

At the outlet of the reactor, a sample of the products of the reactionis taken, washed by a pre-column and analyzed online by a gas phasechromatography equipped with low polarity capillary column.

The analysis by chromatography is carried out using a column CP Sil 8CB,dimensions 50 m*0.32 mm*5 μm. The programming of temperature of the ovenis the following one: 70° C. during 10 min then slope of 10° C./minuntil 250° C.

Considering that xi is the initial amount of moles of raw material andxf the total final amount of moles of raw material, conversion (%) is:(xi-xf)/xi*100. Selectivity of a product is calculated by the ratiobetween the amount of moles recovered of this product and the totalamount of moles of products of reaction.

The molar ratio of HF (MR HF) is defined as the ratio between the molarflow rate of HF and the molar flow rate of 1,1,1,2,3-pentachloropropane.

Example 1

Fluorination of 240 db (1,1,1,2,3-pentachloropropane) is performed inthe reactor described above with 79.4 cm³ of Ni—Cr catalyst supported onAlF₃.

The catalyst used is a mixed catalyst nickel/chromium of atomic ratio ofNi/Cr=1, supported on alumina fluoride and is prepared by impregnatingsolutions of nickel and chromic anhydride (CrO₃). After impregnation anddrying, the solid is treated at a temperature between 320° C. and 390°C. in the presence of a mixture of hydrofluoric acid and nitrogen(concentration by volume of 5 to 10% of this acid in nitrogen).

The reactor was continuously fed with 15 g/hr of anhydrous HF and about4.5 g/hr of 1,1,1,2,3-pentachloropropane at atmospheric pressure for 86hrs. Thus, the contact time is 7.4 seconds, the molar ratio of HF to 240is 36, and the reaction temperature is 340° C. The amount of oxygen isabout 4 mol % with respect to the 240 db. Results are given in the table1.

Example 2

Fluorination of the mixture of 65.9 mol % of 240 db or1,1,1,2,3-pentachloropropane and 34.9 mol % of 240aa or1,1,2,2,3-pentachloropropane is performed according to example 1described above. The reactor was continuously fed with 16 g/hr ofanhydrous HF and about 5.1 g/hr of 1,1,1,2,3-pentachloropropane atatmospheric pressure. Thus, the contact time is 6.9 seconds, the molarratio is 34, and the reaction temperature is from 340° C. The amount ofoxygen is about 4 mol % with respect to the total number of mole of1,1,1,2,3-pentachloropropane and 1,1,2,2,3-pentachloropropane. Resultsare given in table 1.

Examples 3 and 4

Example 2 is repeated at different temperatures as indicated in table 1.

TABLE 1 Selectivity (Area (%)) Temp. Conversion 1234yf + ° C. % 245cb1233xf others Ex. 1 340 100% 1.6 98.3 0 Ex. 2 340 100% 0.5 72.0 25.6 Ex.3 360 100% 0.5 72.0 25.1 Ex. 4 380 100% 0.6 74.3 22.8

No deactivation is seen in example 1 after 86 hours. Further, it isremarkable that the selectivity remains very high

1. Process comprising the catalytic fluorination in the gas phase of1,1,1,2,3-pentachloropropane and/or 1,1,2,2,3-pentachloropropane into2-chloro-3,3,3-trifluoropropene in the presence of Hf, a catalyst andoxygen.
 2. Process according to claim 1, wherein the ratio of oxygenwith respect to 1,1,1,2,3-pentachloropropane and/or1,1,1,2,2,3-pentachloropropane is 0.05 to 15 mole.
 3. Process accordingto claim 1 wherein said catalyst comprises Ni—Cr, preferably supported.4. Process according to claim 1, wherein said catalyst is supported on asupport selected from fluorinated alumina, fluorinated chromia,fluorinated activated carbon or graphite carbon.
 5. Process according toclaim 1, wherein said catalyst further comprises a co-catalyst selectedfrom Ni, Co, Zn, Mn or mixtures thereof and wherein said co-catalyst ispresent in an amount from about 1-10 wt % of said catalyst.
 6. Processaccording to claim 1, wherein said catalyst is activated with afluorine-containing compound.
 7. Process according to claim 1, in whichsaid 1,1,1,2,3-pentachloropropane contains up to 40 mol % of1,1,2,2,3-pentachloropropane.
 8. Process according to claim 1, carriedout at a pressure from 1 to 20 bars.
 9. Process according to claim 1,carried out at a temperature of from 200 to 450° C.
 10. Processaccording to claim 1, carried out with a contact time from 6 to 100 sec.11. Process according to claim 1, carried out at a molar ratio of1,1,1,2,3-pentachloropropane and/or 1,1,2,2,3-pentachloropropane to HFof from 3:1 to 150:1.
 12. Process according to claim 1, carried out inthe presence of a polymerization inhibitor.
 13. The process according toclaim 1 which is continuous.
 14. Process according to claim 1, whereinthe ratio of oxygen with respect to 1,1,1,3-pentachloropropane and/or1,1,2,2,3-pentachloropropane is 0.5 to 10 mole %.
 15. Process accordingto claim 6, wherein said fluorine-containing compound is hydrogenfluoride.
 16. Process according to claim 6, wherein said catalyst isactivated at a pressure above 10 bars.
 17. Process according to claim 1,carried out at a pressure from 3 to 15 bars.
 18. Process according toclaim 1, carried out at a pressure from 5 to 10 bars.
 19. Processaccording to claim 1, carried out at a temperature of from 300 to 430°C.
 20. Process according to claim 1, carried out at a temperature offrom 320 to 420° C.
 21. Process according to claim 1, carried out with acontact time from 10 to 80 sec.
 22. Process according to claim 1,carried out with a contact time from 15 to 50 sec.
 23. Process accordingto claim 1, carried out at a molar ratio of 1,1,1,23-pentachloropropaneand/or 1,1,2,2,3-pentachloropropane to HF of from 4:1 to 70:1. 24.Process according to claim 1, carried out at a molar ratio of1,1,1,2,3-pentachloropropane and/or 1,1,2,23-pentachloropropane to HF offrom 5:1 to 50:1.
 25. Process according to claim 12 wherein saidpolymerization inhibitor is chosen from the group consisting ofp-methoxyphenol, t-amylphenol, limonene, quinones, hydroquinones,epoxides, amines and mixtures thereof.